WO2008132051A1 - Composition thermoréactive et procédé de fabrication - Google Patents

Composition thermoréactive et procédé de fabrication Download PDF

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Publication number
WO2008132051A1
WO2008132051A1 PCT/EP2008/054595 EP2008054595W WO2008132051A1 WO 2008132051 A1 WO2008132051 A1 WO 2008132051A1 EP 2008054595 W EP2008054595 W EP 2008054595W WO 2008132051 A1 WO2008132051 A1 WO 2008132051A1
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Prior art keywords
isocyanate
polymer
solid
temperature
micronized
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PCT/EP2008/054595
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German (de)
English (en)
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Thomas Abend
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Thomas Abend
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/798—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing urethdione groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0895—Manufacture of polymers by continuous processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3228—Polyamines acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/60—Polyamides or polyester-amides
    • C08G18/603—Polyamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2120/00—Compositions for reaction injection moulding processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2140/00—Compositions for moulding powders
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2150/00—Compositions for coatings
    • C08G2150/20—Compositions for powder coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2170/00—Compositions for adhesives
    • C08G2170/20—Compositions for hot melt adhesives

Definitions

  • thermoreactive compositions especially hot-melt hot melt adhesives containing at room temperature solid, in particular micronized (di- / poly) isocyanates and polymers which are solid at room temperature and having isocyanate-reactive groups.
  • the aim is to reduce the energy for the production, to lower the crosslinking temperature, to increase the crosslinking speed in order to reduce the energy expenditure.
  • substrates with limited heat resistance can be bonded or coated.
  • Tm melting or softening temperature of the functional polymers
  • Tc crosslinking or reaction temperatures
  • Tm Softening temperature
  • Tc crosslinking temperature
  • Isocyanate-based, thermo-active compositions which are commercially available are predominantly prepared by mixing and extruding functional polymers with a crosslinking agent, for example blocked isocyanates, in an extruder, the softening or melting point of the polymers (Tm) being 20 0 C to 40 0 C must be below the reaction or crosslinking temperature (Tc) of the crosslinking agent.
  • Tm melting temperature
  • Tc crosslinking temperature
  • the polymer can be mixed in the thermoplastic state above its melting temperature (Tm) and below the crosslinking temperature (Tc) with the crosslinker (and other additives, pigments, adhesion promoters, etc.).
  • Tm melting temperature
  • Tc crosslinking temperature
  • the mass is again cooled below the melting point (Tm), where it solidifies. Subsequently, the solid extrudate is ground and sifted into the desired fractions.
  • solid reactive hot-melt adhesive powders according to EP 598 873 or EP 1 231 232.
  • solid, micronized of deactivated polyisocyanate is dispersed in a liquefied hyroxyfunk- tional polymer at temperatures of 75 0 C to 80 0 C and the mixture cooled back to room temperature during the preparation.
  • the softening or melting temperature of the functional polymer (Tm) by 20 0 C to 40 0 C. below the onset temperature of the crosslinking reaction (Tc) of the fixed, desak- TiVi Erten isocyanate.
  • Tc crosslinking reaction
  • the solidified masses are ground and spotted in the desired fractions.
  • This reactive Hot melt adhesive cross-link in a temperature window of 100 ° C to 150 0 C. characteristics of the mentioned method for producing the reactive hot-melt adhesive systems is that they are produced in liquefied isocyanate-reactive polymers at elevated temperatures.
  • the reaction or crosslinking temperature (Tc) of the solid microbial isocyanates does not necessarily correspond to the melting temperature of the powdery polyisocyanate.
  • the reaction or crosslinking temperature (Tc) of the system is influenced by its solubility in the liquefied polymer, by plasticizers and other polar components of the mixture, by catalysts, by grain size distribution, by possible surface deactivation, by varying amounts of polyamines.
  • the stabilizing surface deactivation of micronised solid isocyanates is u. a. described in EP 062 780, EP 103 323 and EP 922 720; reference is made to this.
  • the light-off temperature may also be at much lower temperatures.
  • Dimeric TDI (TDI-U) is predominantly crystalline, but dissolves in liquefied polymers even from temperatures between 80 0 C and 90 0 C and reacts with isocyanate-reactive groups, the reaction rate is low.
  • the light-off temperature (Tc) increases by 5 0 C to 30 0 C.
  • Technically interesting crosslinking rates are achieved from 110 to 120 0 C. See also "Estimating the lifetime of bonded joints", D. Ferrand in Symposium Proceedings Swiss Bonding 06, Ed. (Ed.) Schindel-Bidinelli, Swibotech 2006, pages 295-303.
  • IPDI-T a polymeric aliphatic isocyanate having a functionality of 3-4, is a predominantly amorphous solid.
  • IPDI-T is at a glass transition temperature Tg of about 65 0 C in an extremely viscous liquid, which melts in the range of 105 0 C to 115 0 C to a low-viscosity liquid.
  • Tg glass transition temperature
  • the viscosity of the polymer melt must be low. This means that the polymer melt is brought to a temperature which is in any case 20 ° C. to 30 ° C. above the melting or softening temperature of the solid polymers (Tm).
  • Tm melting or softening temperature of the solid polymers
  • the temperature of the polymer melt about 80 0 C to 90 0 C.
  • thermoreactive hotmelt adhesive with which reduces the energy for the production, lowered the crosslinking temperature and / or increased crosslinking speed can.
  • thermo-reactive composition comprises the steps of: a) providing at least one, in particular micronized, diisocyanate or polyisocyanate which is solid at 20 ° C. and 1013 hPa; b) providing at least one in particular pulverulent polymer having isocyanate-reactive groups; c) preparing a homogeneous mixture comprising at least the di- or polyisocyanate and the polymer; d) compression of the mixture into moldings; e) optional, crushing or grinding the moldings; wherein the polymer is substantially not melted in the presence of the di- or polyisocyanate.
  • isocyanate or "isocyanates” is used for molecules having at least two or more NCO groups, especially for diisocyanates and polyisocyanates.
  • the isocyanate is preferably no temperature> 75 0 C, preferably> 60 ° C exposed to during production of the thermo-responsive composition.
  • the isocyanate is thus possible to use in particular reactive polymers whose softening or melting point is less than 40 0 C below, preferably less than 20 0 C below the reaction temperature of the isocyanate, more preferably even equal to or greater than the reaction temperature (Tc) of the isocyanate.
  • Tc reaction temperature
  • micronized or “micronization” is meant here and in the following: All those processes which lead to solid powdery polymers having particle sizes below 300 microns, such as grinding, Cryomahlung, spray drying of solutions or dispersions, spray solidification of polymer melts, spray granulation, freeze drying, precipitation the polymers from solutions, sifting or sieving of fractions with particle sizes below 300 microns, starting from coarser powders.
  • micronization is limited to milling and sifting or classification.
  • a method is preferably dry pressing agglomeration is very particularly preferably in step d) is applied, preferably at temperatures in the range of about 10 0 C to 75 ° C, preferably in the range of about 20 0 C to 60 0 C.
  • compositions obtained by compaction according to the invention differ in particular by their density from compositions obtained by heating the components to temperatures above the softening or melting point.
  • density By remaining inclusions of air in the compression compositions are obtained, which - with otherwise the same chemical composition - at least by 1%, typically at least 2%, often up to 5% lower density than compositions that under heating of the components to temperatures above the softening or melting point.
  • the determination of density in this context is based on the Archimedean principle (buoyancy method); corresponding density determination kits for scales are available, for example, from Mettler-Toledo Intl. Inc.
  • - Hydraulic presses tableting machines.
  • a pressure on the powder mixture resp. the pressure in the range of 10 - 750 N / mm 2 , preferably 15 to 350 N / mm 2 can act.
  • the maximum pressing pressure on the pressing can take up to 10 seconds.
  • the presses are preferably used in the range of possible compression pressures, which ensure the provision of solid compacts with minimal pore volume; suitable compression pressures can be easily determined in standard routine routine tests.
  • Parts of the presses or rollers which come into contact with the product may be thermostated or cooled.
  • the optimal pressure on the roller, the peripheral speed and the temperature, respectively the pressure per area during the compaction in the tableting press, must be determined by usual routine tests.
  • the plastic, viscoelastic and elastic properties as well as the flow point of each polymer and each polymer blend are different.
  • the solid isocyanates are more or less crystalline or amorphous, they should be below the melting or glass transition temperature Tg in the compaction.
  • Tg melting or glass transition temperature
  • the products of the press agglomeration such as pellets, slugs, pellets, briquettes, tablets are then optionally crushed, ground and sifted or sieved into the desired fractions.
  • the ground compacting products are classified into fractions having the following limits: 0-80, 0-125, 0-160, 80-160, 0-200, 80-200, 200-300, 0-500, 200 to 500, 300 to 500, 0 to 600 ⁇ m.
  • the methods and installations are known to the person skilled in the art.
  • Products based on polymers having softening or melting temperatures (Tm) of about 60 0 C to 70 ° C can be ground at room temperature at softening or melting temperatures (Tm) of less than 70 0 C to 60 0 C must usually Cryogenvermah- lung with Help of liquid nitrogen or solid carbonic acid can be applied.
  • Tm softening or melting temperatures
  • the precipitated fractions can be fed back to the press agglomeration.
  • Additives for the flowability of the powders can be added.
  • the large contact area between solid polyisocyanate and polymer accelerates the diffusion of the crosslinking agent in the liquefied polymer and the reactions with the isocyanate-reactive groups of the polymer.
  • the close contact with the solid and liquid polar polymer can also lower the light-off temperature of the crosslinking reaction (Tc), while the crosslinking reaction by catalysts can be accelerated.
  • the latent-reactive shaped bodies, agglomerates or powders formed after the press agglomeration and, if necessary, the milling are stable in storage at room temperature for at least 4 months. They are outstandingly suitable as hotmelt adhesives, but can also be used, for example, if appropriate after application-specific modification, for (powder) coatings, powder coatings, as sintering powder for the slush molding process, or the like.
  • the particle sizes, particle size distributions, distribution sums and the specific surfaces are determined and calculated according to the methods of laser diffraction with devices from Sympatec Helios, Quantachrome CILAS, Malvern Mastersizer and other suppliers.
  • the volume-based particle size distribution assumes a density of 1.0 g / cm 3 as the density of the polymers and polyisocyanates. Measurements with such devices under standard conditions, unless explicitly stated otherwise, are referred to herein.
  • the solid, in particular micronized, isocyanate has an arithmetically averaged particle size d 50 in the range from about 0.01 ⁇ m to about 25 ⁇ m, preferably in the range from about 0.1 ⁇ m to about 10 ⁇ m.
  • both a) solid micronized polyisocyanates; as well as b) solid micronized surface-deactivated polyisocyanates can be used for the purpose according to the invention.
  • storage-agglomerated and latently hot-curing mixtures of isocyanate-reactive polymers with solid micronized polyisocyanates are obtained by press-agglomeration of mixtures with pulverulent isocyanate-reactive polymers at room temperature.
  • the extrusion of reactive polymers with isocyanates known from the prior art would lead to premature crosslinking in the case of unblocked isocyanates.
  • the present invention thus opens up a wider range of applications.
  • the stabilizing surface deactivation of micronised solid isocyanates is u. a. described in EP 062 780, EP 103 323 and EP 922 720. This can also serve to increase the light-off temperatures for crosslinking reactions (Tc) in comparison to non-deactivated solid isocyanates.
  • the concentration of the deactivating agent should generally be 0.1 to 25, preferably 0.5 to 10 equivalent percent, based on the totality of the isocyanate groups present.
  • the surface stabilization reaction can be carried out on various kinds of materials
  • thermo-active composition in particular a hot-melt adhesive obtainable by a method as set forth above.
  • a composition contains - at least one solid, in particular micronized di- or
  • Polyisocyanate at least one in particular pulverulent polymer with isocyanate-reactive groups; wherein the isocyanate and the polymer are present melt-free and essentially unreacted combined.
  • the softening or melting point (Tm) less than 40 0 C below the polymer, preferably less than 20 0 C below the reaction temperature (Tc) of the isocyanate a) is particularly preferably equal to or greater than the reaction temperature (Tc) of the isocyanate.
  • thermoreactive composition described above as a hot melt adhesive.
  • Polyisocyanates all di- or polyisocyanates or mixtures thereof are certainly useful in the invention provided they have a melting point of at least 35 0 C (at 1013 hPa) and can be converted by known methods in powder form with average particle sizes dso of less than 25 microns. They may be aliphatic, cycloaliphatic, heterocyclic or aromatic polyisocyanates.
  • powder coating hardeners with free isocyanate groups according to EP 254 152, or mixtures thereof are mentioned in particular: Melting point isocyanate o Ji L ⁇ J ___
  • TDI-U Naphthalene-1, 5-diisocyanate (NDI) 131 dimeric TDI, dimeric 1-methyl-2, 4-phenylene diisocyanate (TDI-U)
  • crosslinking temperature (Tc) of the solid isocyanate can be chosen higher or lower than the glass transition temperature (Tg) or the softening or melting temperature (Tm) of the functional one polymer. It is also possible to use amorphous polyisocyanates, both aromatic and aliphatic.
  • urethane catalysts are organic tin, iron, lead, cobalt, bismuth, antimony, zinc, aluminum, titanium and zirconium compounds.
  • Tertiary amines such as dimethylbenzylamine, diazabicyclooctane (DABCO), diazabicycloundecene (DBU) or diazabicyclononene (DBN), as well as non-volatile polyurethane foam catalysts based on tertiary amine can be used for specific purposes or in combination with metal catalysts, but the catalytic activity of the amines can be impaired by reaction with the carbon dioxide in the air.
  • concentration of the catalysts is usually in the range of 0.001% to 3%, preferably 0.01% -1% based on the reactive system.
  • the catalysts can be added in micronized form to the powder of the polymers, dissolved in the polymer with the isocyanate-reactive groups, adsorbed on micronized silica or molecular sieve powder are added to the polymer powder, or sprayed onto the powder mixture.
  • Suitable reaction partners of the solid micronized isocyanates according to the invention are polymers which are solid at room temperature and carry isocyanate-reactive functional groups which may be terminal or pendant. At least 2 functional isocyanate-reactive groups should be present per molecule.
  • the polymers contain from 0.1 to about 40, preferably from 0.2 to 20, percent by weight of isocyanate-reactive groups, such as hydroxyl, phenolic hydroxyl, amino, carboxyl, amide, urethane and urea groups.
  • Aminofunctional polymers have the advantage that they can be crosslinked in wet or moist conditions (without secondary reaction by water) with the solid micronized isocyanates.
  • the molecular weight of Polmyers is typically in the range of 500 to 1 '000 1 OOO Da, preferably in the range of 1000 to 100' 000 Da.
  • the melting point or softening range (Tm) of the polymer or polymer mixture is typically in the temperature range from 40 0 C to 140 0 C.
  • the glass transition temperature (Tg) of polymers eg. For powder coatings should normally not be practical reasons below 40 ° C.
  • the ratio of the equivalents between the isocyanate groups in the finely divided polyisocyanates and the sum of the hydroxyl, Amino groups and further isocyanate-reactive groups of the polymers should generally be in the range 0.01 to 100, preferably 0.1 to 10, very particularly preferably 0.5 to 5.
  • Suitable polymers or copolymers with isocyanate-reactive groups for example polyvinyl alcohol, partially hydrolyzed EVA or polyvinyl acetate, PVC copolymers with hydroxyl groups, ethylene copolymers, polyvinyl formal, solid polyols such as polytetrahydrofuran, hydrogenated polybutadiene diols or vegetable oils with hydroxyl groups (including dimerized) , Hydroxyethyl or hydroxypropylcellulose, hydroxy-functional crystalline or amorphous polyesters, polycaprolactones and their copolyesters, polycarbonates, thermoplastic polyurethanes and polyureas, amino resins, melamine resins, polyamidoamines, copolyamides which carry hydroxyl, primary or secondary amino groups or acid groups, polyesteramides, phenoxy resins, poly ( meth) acrylates or copolymers, higher molecular weight solid epoxy resins or their solid amine adducts, Michael addition products of
  • the isocyanate-reactive polymers are preferably brought into powder form by known methods, with particle sizes from 0 to 300 .mu.m, preferably from 0 to 160 .mu.m, very particularly preferably from 0 to 80 .mu.m, wherein the specified limits are to comprise 96% of the distribution sum Q.
  • the methods for this are state of the art. These are essentially: a) Grinding or cold grinding of polymers which are in the form of coarse powders, pastilles, granules. b) extrusion of molten polymers, subsequent cooling below the softening point, comminution and grinding to the desired powder. c) polymerization or polyaddition of monomers or their mixtures in solution, dispersion, emulsion or suspension, followed by isolation in powder form, for example by spray-drying at elevated temperatures, filtration or centrifugation, and subsequent drying. d) dissolving the polymers in a solvent at room temperature or elevated temperature, followed by precipitation by reducing the temperature or adding a non-dissolving liquid. e) sieving of coarse polymer powders and isolation of fractions with particle sizes below 300 ⁇ m.
  • Additives can be added to the polymers, the micronized isocyanates or the powder mixture thereof. Aggregates may be mixed in the abovementioned components, dissolved, dispersed or adsorbed on micronized silicates and molecular sieve powder. Liquid additives or those dissolved in water, solvents or plasticizers can also be sprayed onto one of the components with micro-spray systems.
  • the aggregates and their mixtures can be selected from the group consisting of liquid and solid plasticizers, oils, waxes, resins, leveling and substrate wetting agents, degassing and deaerating agents, adhesive resins, adhesion promoters, organic or inorganic fillers, nanoscale fillers, polyanilines, carbon black, Graphite, carbon fibers, fibers, micronised metals or metal oxides, ferrites, barium or lead titanates or zirconates, piezoelectric particles, magnetic particles, thermoplastic polymer powders, pigments, dyes, light stabilizers, aging stabilizers or antioxidants, acid scavengers, corrosion inhibitors mittein, flame retardants, blowing agents, organofunctional silanes, low molecular weight liquid or solid amino- or hydroxy-functional compounds (such as isophthalic dihydrazide, pentaerythritol). Optimal amounts, effects and benefits of the additives are known in the art.
  • Polyol powder, micronized solid isocyanates and, where appropriate, additives are combined prior to press agglomeration into a powder mixture that is as homogeneous as possible, if possible with a random distribution as far as possible.
  • the used equipment is state of the art. The methods are described in Handbook of Powder Science and Technology; edited by M.E. Fayed and L. Otten, Van Nostrand Reinhold Comp .; New York, 1984. Mixing in the Process Industries; Ed. by N. Harnby, M.F. Edwards, A.W. Nienow; Butterworth and Heinemann; London, 1992. Powder Mixing; B. Kaye; Chapman & Hall, London, 1997. Handbook of Industrial Mixing: Science and Practice; edited by E.L. Paul, et al .; John Wiley and Sons, New York, 2004.
  • the quality of the mixture depends on the properties of the components such as density, mixing ratio, particle size differences, particle shape, average particle size, particle size distribution, surface structure and the type of mixer.
  • the processes may be continuous or discontinuous and depend on whether individual fractions or the powder mixture are free-flowing or cohesive.
  • the tablets can also be used without comminution as reactive hotmelt tablets for bonding or sealing.
  • suitable shaping processes it is also possible to produce (unreacted) profiles, tapes or other compacts from the powder mixtures or press agglomerates.
  • the storage of the products or powder takes place at room temperature.
  • the powder mixtures according to the invention are stable at room temperature for at least 4 months.
  • the surfaces can be provided with micronized silicas as release agents.
  • the products are solid in the uncrosslinked state and preferably tack-free.
  • the shaped bodies or powders are packaged in water or gas impermeable packaging.
  • Crosslinking occurs upon exposure to heat at temperatures above the melting temperature or softening range (Tm) of the isocyanate-reactive polymer and above the glass transition (Tg) or melting temperature (Tm) of the solid isocyanate.
  • Tm melting temperature
  • Tm melting temperature
  • Tm melting temperature
  • Tm melting temperature
  • Tm melting temperature
  • the curing conditions or curing windows in the heat, as well as the post-crosslinking at room temperature must be determined experimentally; Such attempts are routine routine.
  • a particular advantage of the system according to the invention is that, after initiating the crosslinking reaction in the heat and forming a liquid polymer film, the curing reaction also persists after cooling to room temperature (Postcure). Up to 90% of the final strength is reached after about 1 to 7 days, depending on the composition of the product. Low Tg of the polymer, of the polyisocyanate, polar impurities and catalysts accelerate postcrosslinking.
  • thermoreactive compositions according to the invention can, if appropriate after application-related modification, also be processed as powder coatings; they differ from the commercially available powder coatings by a very low attainable crosslinking temperature resp. high crosslinking speed.
  • the low stoving temperatures save energy.
  • the low crosslinking temperature allows the application on heat-sensitive substrates, such as plastics, Wood, MDF panels, foams, etc. Deep cross-linking temperature is also beneficial in the case of metals which show embrittlement and solidification at higher stoving temperatures.
  • the application and crosslinking of the inventive reactive hot melt adhesive is carried out directly or after previous sintering on surfaces of the substrate.
  • the temperature to which the reactive powder is sintered on the surface is to about 5 to 15 0 C above the melting temperature or the softening range of the polymer. After sintering, it is immediately cooled again, the pre-coating can be stored at room temperature for at least 2 months.
  • the latently reactive powders can also be used in the form of a dispersion in aqueous or solvent-containing film-forming systems.
  • the condition is that the liquid phase has virtually no solution effect on the powdered reactive hot melt adhesive or the powder coating. Otherwise, the use of deactivated solid isocyanates is recommended.
  • soluble reactive or non-reactive binders and additives may be added. Such preparations can be crosslinked after evaporation of the solvent or water at elevated temperature immediately or after prolonged storage.
  • the pulverulent reactive hotmelt adhesives according to the invention can also be dispersed in monomer-free isocyanate prepolymers and UV-crosslinking prepolymers, pressure-sensitive adhesives and other liquid phases, provided that they are non-dissolving and reactive at room temperature for the powdery reactive hot melt adhesives.
  • the heat input for the thermoplastic processing and for the cross-linking can be done with contact heat, convection heat, hot air or hot gas, resistance heating, ultrasonic heating, vibration heating, friction welding, electromagnetic radiation (for example infrared, induction, microwave, laser radiation).
  • latent heat-reactive melt systems Possible applications for the latent heat-reactive melt systems according to the invention are: adhesives for textiles, nonwovens, films, leather, paper, cardboard, foam, wood, metals, plastics, building materials, ceramic parts or glass, electronic components, laminating adhesives, autoclavable adhesives , Security adhesives for documents, pharmaceutical or food packaging; as well as after application-specific modification:
  • crosslinkable powder coatings their dispersions in water or in nonsolvating solvents, sintering powders, redispersible powders, coatings; - Thermoreactive sintering powders for the slush molding process, for rotational molding, rotational sintering, centrifugal casting, for the production of composite materials, for reactive extrusion and reaction injection molding, hot-crosslinking adhesives for in-mold labeling.
  • the powders were compacted at room temperature with a hydraulic tablet press PP 25, Retsch GmbH, (D-Haan) with a maximum of 25 tons pressing pressure.
  • the following round pressing tools made of stainless steel were used: - diameter 32 mm, maximum pressure on the pressing 244 N / mm 2 at 20 tons of hydraulic pressure on the tablet press. - Diameter 40 mm, maximum pressure on the pressure 156
  • the tablets or slugs were crushed to particle sizes of 1 to 5 mm and minced or submerged at room temperature Addition of liquid nitrogen or solid carbon dioxide cryo- or cold-ground.
  • solid isocyanates and polymers also the solid isocyanates and polymers
  • pin mills or ultracentrifugal mills with matching sieves were used.
  • Beechwood specimens of masses 100 x 20 x 5 mm 3 and aluminum of mass 20 x 100 x 1 mm 3 were simply press-bonded at overlapping temperatures at room temperature and cross-linked at the indicated times and temperatures.
  • the powders having an upper particle size of 80 to 300 ⁇ m to be tested were sprinkled onto the surface of the beechwood test specimens at a rate of 50 to 150 g / m 2 .
  • the test specimens made of wood and aluminum were cross-linked during the indicated times and temperatures in a circulating air oven under slight clip pressure.
  • the specimens were post-crosslinked for 7 to 10 days at room temperature before the test.
  • the specimens were measured vertically in The convection oven hung at 150 0 C and charged with 300 g. Rapid heat transfer is ensured by the one-sided use of aluminum sheet. Loss of adhesion of the adhesive surfaces led to the fall of the weights. The time until the loss of adhesion at 150 0 C was recorded.
  • the powders were applied to silane-primed aluminum and baked in a convection oven for 30 minutes at 95 0 C.
  • the powder coating composition which was applied from aqueous dispersion, was first dried at room temperature.
  • Aromatic diisocyanate, f 2; Isocyanate content 22.5 -24.5%; Melting range 145 to 156 0 C; average particle size d 50 7.5 ⁇ m, 4% ⁇ 1 ⁇ m, 95% ⁇ 18 ⁇ m.
  • IPDI-T 2.1 Desmodur Z XP 2589, (Bayer MaterialScience, D-Leverkusen);
  • Vestanat T 1890/100 (Degussa AG, D-Marl); milled to average particle size d 50 13.8 ⁇ m, 4% ⁇ 1 ⁇ m, 95%
  • Vestanat T 1890/100 (Degussa AG, D-Marl); milled to mean particle size d 50 8.2 ⁇ m, 4% ⁇ 1 ⁇ m, 95%
  • Hydroxyfunctional linear polycaprolactone Solvay caprolactones, UK Warrington
  • Capa 6100 Hydroxy functional linear polycaprolactone (Solvay Caprolactones, UK Warrington);
  • Hydroxy functional polycaprolactone Solvay Caprolactones, UK Warrington); Molecular weight 8,000 Da, functionality 4; Melting point 40 - 50 0 C, hydroxyl value 28 mg / KOH / g, Cryogemahlen for powder with fraction 0-80 microns, ⁇ 4% above 80 microns.
  • thermoplastic polyurethane (Bayer MaterialScience, D-Leverkusen); Melting point 50 ° C., strongly crystallizing, the fraction 0-100 ⁇ m, ⁇ 4% over 100 ⁇ m, was used. Assumed OH equivalent 3500 g / Eq.
  • Amino-terminated copolyamide (Degussa AG, D-Marl); Melting range 110-125 0 C, molecular weight about 6600 Da, NH- Equivalent 3300 g / eq. , ground to powder 0 - 80 ⁇ m, ⁇ 4% over 80 ⁇ m.
  • Trifunctional aliphatic amine (Huntsman, B-Everberg); NH equivalent 146 g / eq.
  • Dicyclohexyl phthalate (Lanxess AG, D-Leverkusen); Plasticizer, melting point 64 0 C, powder 0 - 40 microns.
  • Tegokat P-128 dibutyltin dilaurate, 75% on micronised silica (Goldschmidt TIB, D-Mannheim); free-flowing powder, catalyst for the isocyanate-hydroxyl reaction.
  • Solid isocyanate Type Average particle size ⁇ m phr: Additive to 100 parts polymer Additives: Type; amount
  • Agglomeration conditions a) tablet press; Press pressure; in N / mm 2 or MPa b) Continuous two-roll compaction machine; Pressure on rollers in kN / cm
  • Polymer Desmomelt VP KA 8702; hydroxyl-termxmertes polyester polyurethane, 0 - 100 microns, melting point 50 0 C.
  • Polymer Polycaprolactone CAPA 2803, ground to particle sizes smaller than 80 ⁇ m
  • the powder coating was ground to a particle size of less than 125 microns, about 100 g / m 2 was applied and burned on (with Silangemisch gep ⁇ mertes) aluminum.
  • the powder coating formulation according to experiment 8 with a particle size of less than 125 ⁇ m, was dispersed in water with 0.1% Tergitol TMN-6 as wetting agent.
  • the watery dispersion was, with a dry weight of about 100 g / m 2, applied to (primed with silane) aluminum, dried at room temperature, and baked 0 C during 30 minutes at 95 and crosslinked.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne un procédé de fabrication d'une composition thermoréactive, comprenant les étapes suivantes : a) mise à disposition d'au moins un diisocyanate ou polyisocyanate solide, notamment micronisé; b) mise à disposition d'au moins un polymère notamment pulvérulent, avec des groupes réactifs avec l'isocyanate; c) préparation d'un mélange homogène, comprenant au moins l'isocyanate et le polymère; d) compression du mélange pour former des pièces moulées; e) en option, fragmentation ou broyage des pièces moulées; le polymère n'étant sensiblement pas fondu en présence de l'isocyanate. Dans le cadre de la présente invention, on peut se passer de manière particulièrement avantageuse d'un procédé d'extrusion au cours duquel le polymère serait fondu. Ainsi, le coût énergétique de la préparation est réduit, et l'on dispose aussi d'un choix plus grand d'isocyanates, à savoir ceux qui conduiraient déjà, dans des conditions d'extrusion usuelles, à l'amorce d'une réaction de réticulation.
PCT/EP2008/054595 2007-05-01 2008-04-16 Composition thermoréactive et procédé de fabrication WO2008132051A1 (fr)

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EP07107296A EP1988111A1 (fr) 2007-05-01 2007-05-01 Composition thermoréactive et son procédé de fabrication
EP07107296.1 2007-05-01

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110288242A1 (en) * 2010-05-20 2011-11-24 A. Raymond Et Cie Adhesive polyurethane powder capable of being activated by heat

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102012203249A1 (de) * 2012-03-01 2013-09-05 Tesa Se Verwendung eines latentreaktiven Klebefilms zur Verklebung von eloxiertem Aluminium mit Kunststoff
DE102014222259A1 (de) * 2014-10-31 2016-05-04 Tesa Se Verklebung zweier Substrate mittels latentreaktiver Klebefilme
CN112979900B (zh) * 2019-12-18 2022-08-05 万华化学集团股份有限公司 聚氨酯或聚氨酯-脲的水分散体及其制备方法和用途

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0431413A2 (fr) * 1989-12-06 1991-06-12 Bayer Ag Poudre réactive thermodurcissable à partir de polyuréthanes
EP1231232A1 (fr) * 2001-02-12 2002-08-14 Jowat Lobers & Frank Gmbh & Co. Kg Elément adhésif réactif thermofusible autoportant et son utilisation
WO2004014975A1 (fr) * 2002-07-30 2004-02-19 Abend Thomas P Procede et composition pour la fabrication de masses thermofusibles reactives a base d'isocyanates solides a desactivation de surface et de polymeres a groupes fonctionnels

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0431413A2 (fr) * 1989-12-06 1991-06-12 Bayer Ag Poudre réactive thermodurcissable à partir de polyuréthanes
EP1231232A1 (fr) * 2001-02-12 2002-08-14 Jowat Lobers & Frank Gmbh & Co. Kg Elément adhésif réactif thermofusible autoportant et son utilisation
WO2004014975A1 (fr) * 2002-07-30 2004-02-19 Abend Thomas P Procede et composition pour la fabrication de masses thermofusibles reactives a base d'isocyanates solides a desactivation de surface et de polymeres a groupes fonctionnels

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110288242A1 (en) * 2010-05-20 2011-11-24 A. Raymond Et Cie Adhesive polyurethane powder capable of being activated by heat
US9133377B2 (en) * 2010-05-20 2015-09-15 A. Raymond Et Cie Adhesive polyurethane powder capable of being activated by heat

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